CN108906081B - Preparation method and application of multifunctional suspension bed catalyst - Google Patents
Preparation method and application of multifunctional suspension bed catalyst Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/10—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles
- C10G49/12—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 with moving solid particles suspended in the oil, e.g. slurries
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1077—Vacuum residues
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1096—Aromatics or polyaromatics
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- General Chemical & Material Sciences (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a preparation method and application of a multifunctional suspension bed catalyst, which can be applied to kerosene co-refining reaction or heavy inferior oil lightening reaction. The multifunctional high-efficiency catalyst consists of a catalytic cracking functional component and a catalytic hydrogenation functional component. The catalytic cracking functional component of the catalyst is composed of acidic high specific surface active carbon which is loaded with one or more active components selected from Fe, Ni and Zr and is simultaneously treated by one or more acids selected from nitric acid, sulfuric acid and phosphoric acid; the catalytic hydrogenation functional component of the catalyst is composed of high specific surface active carbon loaded with a certain amount of alpha-FeOOH and then vulcanized. The catalyst has the advantages of low cost of the preparation raw materials, simple preparation process, excellent hydrogenation and cracking performance, high yield of light components of the product, wide application range of the raw materials and the like.
Description
Technical Field
The invention relates to preparation of a catalyst, in particular to a preparation method and application of a multifunctional suspension bed catalyst.
Background
The energy structure of China is characterized by rich coal, lack of oil and little gas, limited petroleum resources and external dependence close to 60%. Accelerating the development of clean coal development and high-efficiency utilization technology, and becoming one of the important ways of alleviating the energy safety predicament in China and solving the increasingly prominent ecological environment problem in China. The technical requirements of cleanness, high efficiency and scale in the coal utilization process are increasingly urgent. In addition, with the gradual exploitation and utilization of petroleum resources, the crude oil has obvious heavy weight trend worldwide.
The suspension bed hydrogenation is a leading-edge technology in the field of heavy oil processing, has the characteristic of strong raw material adaptability, and can be used for efficiently upgrading oil coal slurry, heavy oil, coal tar and the like. At present, the suspension bed hydrogenation technology mainly has the problems of high reaction condition severity, prominent abrasion condition, high energy consumption and the like, and the long-period stability and the economic benefit of the device are seriously influenced. In order to solve the problems, the key is to develop a more efficient catalyst for a suspension bed, improve the reaction conversion efficiency and the liquid yield, effectively reduce the reaction severity, and achieve the purposes of reducing the investment, reducing the energy consumption and improving the operation stability.
At present, a great deal of work is done at home and abroad on a suspended bed catalyst, and a plurality of modified components are added on the basis of an iron-based catalyst to improve the reaction performance of the catalyst.
Patent CN104923231A discloses a method for preparing a kerosene co-refining catalyst by precipitation-impregnation, and the obtained catalyst has the advantages of good reaction activity, strong coal liquefaction performance, large specific surface area, and is beneficial to adsorbing metal impurities of raw materials and coke particles generated by reaction and preventing coking.
Patent CN105435831A discloses a microspherical catalyst, which is obtained by impregnating zeolite molecular sieve catalyst microspheres with loaded active metals, and has good cracking performance, desulfurization, denitrification and deoxidation performances when applied to the hydrogenation process of a heavy oil suspension bed.
Patent CN106040288A discloses a suspension bed hydrocracking catalyst, wherein X-type, Y-type or ZSM-5 type molecular sieves are added as cracking active components, and the obtained catalyst has better cracking hydrogenation reaction performance by adjusting the composition ratio.
The research of the patent technologies shows that the reported catalysts all have good reaction effects, but some catalysts have single effects, cannot provide acid centers in the heavy oil hydrocracking process, provide enough cracking performance, have an unsatisfactory overall lightening effect, and other catalysts use high-cost molecular sieves and the like as the acid centers, so that the cost is high. Therefore, it is important to obtain a suspension bed high-efficiency catalyst with good cracking performance and hydrogenation performance by using relatively cheap and easily available raw materials.
Disclosure of Invention
The invention aims to provide a preparation method and application of a multifunctional suspension bed catalyst with catalytic cracking and hydrocracking functions.
In order to achieve the above object, one preparation method of the present invention is a mechanical mixing method:
1) firstly, according to the proportion of 1-100: 1, dissolving strong acid and strong ferrite in deionized water to prepare an acid solution with the acid concentration of 1-16 mol/L;
2) dipping the high specific surface area active carbon into the acid solution obtained in the step 1), and then taking out and drying to obtain an acidified carrier A;
3) mechanically mixing the carrier A and alpha-FeOOH/C according to the mass ratio of 0.1-1:1 to obtain a catalyst precursor;
4) adding a catalyst precursor into a reactor along with reaction raw materials according to the mass ratio of 0.3-3% of the reaction raw materials, and carrying out in-situ vulcanization on a vulcanizing agent added into the raw materials according to the mass ratio of 1:1-10 of sulfur to the catalyst to obtain the catalyst.
The strong acid is one or a mixture of more than one of concentrated sulfuric acid, concentrated nitric acid and concentrated phosphoric acid in any proportion.
The strong ferrite is one or a mixture of more than one of ferric sulfate, ferrous sulfate, ferric phosphate and ferric nitrate in any proportion.
The specific surface area of the activated carbon with the high specific surface area is 200-300m2The dipping time is 1-12 h.
The vulcanizing agent is sulfur powder and CS2Or H2S。
The other preparation method of the invention is a sulfuration acidification method:
1) taking alpha-FeOOH/C solid powder and a vulcanizing agent according to the weight ratio of 1-10: 1, mixing the raw materials in a mass ratio, and vulcanizing at 200-500 ℃ for 2-10 h;
2) and (3) dipping the vulcanized powder into an acid solution for aging treatment, and then taking out the treated carrier for drying to obtain the catalyst.
The vulcanizing agent is sulfur powder and CS2Or H2S。
The acid solution is one or a mixture of more than one of concentrated sulfuric acid, concentrated nitric acid and concentrated phosphoric acid with the concentration of 1-16mol/L in any proportion, and the soaking and aging time is 1-12 h.
The multifunctional composite suspended bed catalyst prepared by the preparation method is used for the suspended bed kerosene co-refining reaction or the hydrogenation and lightening reaction of heavy and inferior oil, and the addition amount of the catalyst is 0.3-3% of the mass of reaction materials.
The heavy inferior oil is FCC heavy oil, vacuum residue oil or high temperature coal tar.
The alpha-FeOOH/C adopted by the invention is the alpha-FeOOH/C prepared in the patent (CN 104923231A).
The invention has the following advantages:
1. the catalyst has low production raw material cost and simple preparation process.
2. The catalyst of the present invention has excellent performance, and good hydrogenation and cracking performance.
3. The catalyst has wide raw material application range and high yield of the obtained product light oil product.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1:
preparing a catalyst by adopting a mechanical mixing method: first, the concentrated H is2SO4With FeSO4Preparing an acid solution with a molar ratio of 10:1 of 5mol/L, then soaking 10g of activated carbon in 500ml of the acid solution, stirring at normal temperature, aging for 12 hours, filtering and taking out the treated activated carbon, and drying at 100 ℃ for 12 hours to obtain black solid powder, which is marked as A; the method provided in the patent (CN104923231A) is adopted to synthesize the alpha-FeOOH supported high ratioThe black powder on the surface activated carbon support is designated as B. According to the mass ratio A: and (B) mechanically mixing the two components in a ratio of 1:1 to obtain a catalyst precursor C-1.
Example 2:
preparing a catalyst by adopting a mechanical mixing method: first, concentrated HNO3Concentrated H3PO4With Fe2(SO4)3Preparing an acid solution of 8mol/L according to a molar ratio of 10:10:1, then soaking 10g of activated carbon in 500ml of the acid solution, stirring at normal temperature, aging for 6 hours, filtering and taking out the treated activated carbon, and drying at 100 ℃ for 12 hours to obtain black solid powder, which is marked as A; in addition, black powder with alpha-FeOOH supported on high specific surface active carbon carrier, denoted as B, was synthesized by the method proposed in patent (CN 104923231A). According to the mass ratio A: and B is 1:2, and the two components are mechanically mixed to obtain a catalyst precursor C-2.
Example 3:
preparing a catalyst by adopting a sulfurization acidification method: firstly, synthesizing alpha-FeOOH/C catalyst precursor by the method provided in the patent (CN104923231A), taking 20g of the solid powder, and mixing the solid powder with CS according to the proportion of the alpha-FeOOH/C solid powder2Mixing the raw materials in a mass ratio of 1:1, and treating and vulcanizing at 400 ℃ for 4 h; subsequently, the vulcanized powder was immersed in 500ml of concentrated H2SO4With FeSO4And (3) soaking and aging the carrier in 10mol/L acid solution with the molar ratio of 10:1 at normal temperature for 8 hours, filtering the treated carrier, taking out the carrier, and drying the carrier at 100 ℃ for 12 hours to obtain the catalyst C-3.
Example 4:
preparing a catalyst by adopting a sulfurization acidification method: firstly, synthesizing alpha-FeOOH/C catalyst precursor by the method provided in the patent (CN104923231A), taking 20g of the solid powder, mixing the solid powder with H according to the proportion of the alpha-FeOOH/C solid powder2S, mixing the components in a mass ratio of 10:1, and treating and vulcanizing at 400 ℃ for 2 h; subsequently, the vulcanized powder was immersed in 500ml of concentrated HNO3Concentrated H3PO4With Fe (NO)3)3Soaking and aging the carrier in 5mol/L acid solution with the molar ratio of 10:10:1 at normal temperature for 12h, filtering the treated carrier, taking out the carrier, and drying the carrier at 100 ℃ for 12h to obtain the catalyst C-4.
The prepared catalyst or catalyst precursor is applied to the kerosene co-refining reaction, and the reaction conditions are as follows: the reaction temperature is 460 ℃; the initial pressure of the reaction hydrogen is 9 MPa; the catalyst addition was 1.5 wt.% (based on the reaction starting materials); coal addition 30 wt.%; the vulcanizing agent is sulfur powder; the reaction time was 1 hour. The reaction results are shown in table one.
Example 5:
preparing a catalyst by adopting a mechanical mixing method: first, the concentrated H is2SO4Preparing 1mol/L acid solution with FePO4 according to the molar ratio of 1:1, then soaking 10g of activated carbon in 500ml of the acid solution, stirring at normal temperature, aging for 12h, filtering and taking out the treated activated carbon, and drying at 100 ℃ for 12h to obtain black solid powder, which is marked as A; the black powder with alpha-FeOOH supported on the high specific surface active carbon carrier is synthesized by the method proposed in the patent (CN104923231A), and is marked as B. According to the mass ratio A: and B is 0.1:1, and the two components are mechanically mixed to obtain a catalyst precursor C-5. Adding a catalyst precursor into a reactor along with reaction raw materials according to the mass ratio of 0.5 percent of the reaction raw materials, and carrying out in-situ vulcanization on a vulcanizing agent added into the raw materials according to the mass ratio of 1:1 of sulfur to the catalyst to obtain the catalyst.
Example 6:
preparing a catalyst by adopting a mechanical mixing method: first, the concentrated H is2SO4Preparing 16mol/L acid solution with Fe (NO3)3 according to a molar ratio of 50:1, then soaking 10g of activated carbon in 500ml of the acid solution, stirring at normal temperature, aging for 12h, filtering and taking out the treated activated carbon, and drying at 100 ℃ for 12h to obtain black solid powder, which is marked as A; the black powder with alpha-FeOOH supported on the high specific surface active carbon carrier is synthesized by the method proposed in the patent (CN104923231A), and is marked as B. According to the mass ratio A: and (3) mechanically mixing the two components in a ratio of 0.8:1 to obtain a catalyst precursor C-6. Adding a catalyst precursor into a reactor along with reaction raw materials according to the mass ratio of 3% of the reaction raw materials, and carrying out in-situ vulcanization on a vulcanizing agent added into the raw materials according to the mass ratio of 10:1 of sulfur to the catalyst to obtain the catalyst.
Example 7:
by vulcanizationPreparing a catalyst by an acidification method: firstly, synthesizing an alpha-FeOOH/C catalyst precursor by adopting the method provided in the patent (CN104923231A), taking 20g of the solid powder, mixing the alpha-FeOOH/C solid powder and sulfur powder according to the weight ratio of 10:1, mixing the raw materials in a mass ratio, and treating and vulcanizing at 200 ℃ for 8 hours; subsequently, the vulcanized powder was immersed in 500ml of concentrated HNO3Concentrated H3PO4With FeNO3Soaking and aging 16mol/L acid solution prepared according to the molar ratio of 20:15:15:1 at normal temperature for 1h, filtering and taking out the treated carrier, drying at 100 ℃ for 12h to obtain a catalyst C-7, and adding the catalyst into a reactor along with reaction raw materials according to the mass ratio of 1% of the reaction raw materials.
Example 8:
preparing a catalyst by adopting a sulfurization acidification method: firstly, synthesizing alpha-FeOOH/C catalyst precursor by the method provided in the patent (CN104923231A), taking 20g of the solid powder, and mixing the solid powder with CS according to the proportion of the alpha-FeOOH/C solid powder2Mixing the materials in a mass ratio of 3:1, and treating and vulcanizing at 400 ℃ for 4 h; subsequently, the vulcanized powder was immersed in 500ml of concentrated H2SO4With FeSO4Soaking and aging 1mol/L acid solution prepared according to the molar ratio of 1:1 at normal temperature for 12h, filtering and taking out the treated carrier, drying at 100 ℃ for 12h to obtain a catalyst C-8, and adding the catalyst into a reactor along with reaction raw materials according to the mass ratio of 1% of the reaction raw materials.
The prepared catalyst is applied to the lightening reaction of heavy and inferior oil, and the reaction conditions are as follows: the reaction temperature is 460 ℃; the initial pressure of the reaction hydrogen is 9 MPa; the reaction time was 1 hour. The reaction results are shown in Table II.
TABLE EXAMPLE Effect of kerosene Co-refining reaction
| Catalyst and process for preparing same | Coal conversion (wt.%) | Asphaltene conversion (wt.%) | <Liquid harvest at 525 ℃ (wt.%) |
| C-1 | 89.97 | 88.4 | 80.7 |
| C-2 | 90.15 | 90.7 | 82.4 |
| C-3 | 94.83 | 94.3 | 84.4 |
| C-4 | 91.97 | 91.2 | 81.4 |
TABLE II EXAMPLES Effect of heavy inferior oil lightening reaction
| Catalyst and process for preparing same | Raw oil | Heavy oil conversion (wt.%) | <525℃Liquid harvest (wt.%) |
| C-5 | Anthracene oil | 83.2 | 87.9 |
| C-6 | FCC heavy oil | 82.1 | 89.1 |
| C-7 | Vacuum residuum | 81.5 | 86.3 |
| C-8 | High temperature coal tar | 79.6 | 85.7 |
The foregoing is illustrative of the preferred embodiment of the present invention and is not to be construed as limiting thereof in any way, the scope of the invention being indicated in the claims, and any changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. A preparation method of a multifunctional suspension bed catalyst is characterized by comprising the following steps:
1) firstly, according to the proportion of 1-100: 1, dissolving strong acid and strong ferrite in deionized water to prepare an acid solution with the acid concentration of 1-16 mol/L;
2) dipping the high specific surface area active carbon into the acid solution obtained in the step 1), and then taking out and drying to obtain an acidified carrier A;
3) mechanically mixing the carrier A and alpha-FeOOH/C according to the mass ratio of 0.1-1:1 to obtain a catalyst precursor;
4) adding a catalyst precursor into a reactor along with reaction raw materials according to the mass ratio of 0.3-3% of the reaction raw materials, and carrying out in-situ vulcanization on a vulcanizing agent added into the raw materials according to the mass ratio of 1:1-10 of sulfur to the catalyst to obtain the catalyst.
2. The method for preparing the multifunctional suspended bed catalyst according to claim 1, wherein the method comprises the following steps: the strong acid is one or a mixture of more than two of concentrated sulfuric acid, concentrated nitric acid and concentrated phosphoric acid in any proportion.
3. The method for preparing the multifunctional suspended bed catalyst according to claim 1, wherein the method comprises the following steps: the strong ferrite is one or a mixture of more than two of ferric sulfate, ferrous sulfate, ferric phosphate and ferric nitrate in any proportion.
4. The method for preparing the multifunctional suspended bed catalyst according to claim 1, wherein the method comprises the following steps: the specific surface area of the activated carbon with the high specific surface area is 200-300m2The dipping time is 1-12 h.
5. The method for preparing the multifunctional suspended bed catalyst according to claim 1, wherein the method comprises the following steps: the vulcanizing agent is sulfur powder and CS2Or H2S。
6. A preparation method of a multifunctional suspension bed catalyst is characterized by comprising the following steps:
1) taking alpha-FeOOH/C solid powder and a vulcanizing agent according to the weight ratio of 1-10: 1, mixing the raw materials in a mass ratio, and vulcanizing at 200-500 ℃ for 2-10 h;
2) according to the proportion of 1-100: 1, dissolving strong acid and strong ferrite in deionized water to prepare an acid solution with the acid concentration of 1-16 mol/L;
3) and (3) dipping the vulcanized powder into an acid solution for aging treatment, and then taking out the treated carrier for drying to obtain the catalyst.
7. The method for preparing the multifunctional suspended bed catalyst according to claim 6, wherein the method comprises the following steps: the vulcanizing agent is sulfur powder and CS2Or H2S。
8. The method for preparing the multifunctional suspended bed catalyst according to claim 6, wherein the method comprises the following steps: the acid solution adopts one or a mixture of more than two of concentrated sulfuric acid, concentrated nitric acid and concentrated phosphoric acid with the concentration of 1-16mol/L in any proportion, the strong ferrite is one or a mixture of more than two of ferric sulfate, ferrous sulfate, ferric phosphate and ferric nitrate in any proportion, and the soaking and aging time is 1-12 h.
9. The use of the multifunctional suspended bed catalyst prepared according to claim 1 or 6, characterized in that: the catalyst is used for the kerosene co-refining reaction of a suspension bed or the hydrogenation and lightening reaction of heavy inferior oil, and the addition amount of the catalyst is 0.3-3% of the mass of reaction materials.
10. Use according to claim 9, characterized in that: the heavy inferior oil is FCC heavy oil, vacuum residue oil or high temperature coal tar.
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| TWI302476B (en) * | 2005-07-06 | 2008-11-01 | Ind Tech Res Inst | Cleaning agent of treating acid gas and method for cleaning with the cleaning agent |
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| CN102218319A (en) * | 2011-04-08 | 2011-10-19 | 大连理工大学 | Preparation method of supported FeOOH catalyst, and electro-Fenton waste water treatment system |
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